过硫代碳酸配体[CS_4]^(2-)生成的新方法──[Me_4N]_n[Cu(CS_4)]_n(I)和[Me_4N]_4[Cu_4(CS_4)_4](Ⅱ)的合成与晶体结构

A New Way to Formation of Perthiocarbonate Ligand── Synthesis and Crystal Structures of [Me_4N]_n[Cu(CS_4)]_n(Ⅰ) and [Me_4N]_4[Cu_4(CS_4)_4](Ⅱ)

用硒酚铜簇合物和硫酚铜簇合物 [Me4 N]2 [Cu4 (EPh) 6](E=Se和 S)与 CS2 及少量 S反应 ,分别获得了以过硫代碳酸根 [CS4 ]2 -为配体的 [Me4 N]n[Cu(CS4 ) ]n( )和 [Me4 N]4 [Cu4 (CS4 ) 4]( ) .并用 X射线单晶衍射法测定了它们的晶体结构 . 为二维层状聚合物 , 为四核铜簇阴离子化合物 .并对 [CS4 ]2

The solutions of tetranuclear copper cluster anionic complexes [Me 4N] 2[Cu 4(SePh) 6] or [Me 4N] 2[Cu 4(SPh) 6] in DMF or CH 3CN reacted with CS 2 in the presence of a small amount of S. From the resulting solutions brown black block shaped crystals Ⅰ or brown red block shaped crystals Ⅱ were formed, respectively. Crystal data: (Ⅰ) orthorhombic, space group Pbca, a =1.138 5(4) nm, b = 1 668 3 (4) nm, c =1 092 1(2) nm, V =2 074 2(9) nm 3. μ =2 846 mm -1 , F (000)=1 136 e, D c=1 777 g/cm 3, for Z=8, R =0 054 4 for 1 821 observed reflections; (Ⅱ) tetragonal, space group P42 1c, a =1 395 2(2) nm, b =1 395 2(2) nm, c =1 135 0(2) nm, V =2 209 4(6) nm 3. μ =2 677 mm -1 , \{ F (000)\}=1 136e, D c=1 671 g/cm 3, for Z=8, R =0 064 5 for 1 114 observed reflections.The X ray crystal structure determination indicated that the molecule of the complex Ⅰ consists of a polymeric anion [\{Cu 2(CS 4) 2\}] 2- n and cations [Me 4N] +. In the polymeric anion, the repeated unit is a dinuclear copper complex [Cu 2(CS 4) 2] 2- , which links to four surrounding aggregations through sulfur bridges to form a two dimensional layer structure. The cations [Me 4N] + locate between the layers. The molecule of complex Ⅱ consists of a tetranuclear copper cluster anion with four perthiocarbonate ligands [Cu 4(CS 4) 4] 4- and four cations [Me 4N] +. The four copper atoms form a tetrahedron. One of the sulfur atoms in each CS 2- 4 ligand forms the sulfur bridge with two Cu atoms while the other is coordinated to only one copper.